CN103285845A - Preparation method of graphene oxide wrapped titania microsphere photocatalyst - Google Patents
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- 239000004005 microsphere Substances 0.000 title claims abstract description 37
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 239000008367 deionised water Substances 0.000 claims description 49
- 229910021641 deionized water Inorganic materials 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 48
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000006228 supernatant Substances 0.000 claims description 24
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
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- 235000010344 sodium nitrate Nutrition 0.000 claims description 11
- 239000004317 sodium nitrate Substances 0.000 claims description 11
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims 3
- 238000013019 agitation Methods 0.000 claims 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims 2
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- 239000004408 titanium dioxide Substances 0.000 description 23
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 14
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- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
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- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域technical field
本发明属于复合材料制备技术领域，涉及一种氧化石墨烯包裹二氧化钛微球材料的制备方法，具体涉及一种氧化石墨烯包裹二氧化钛微球光催化剂的制备方法。The invention belongs to the technical field of composite material preparation, and relates to a preparation method of a graphene oxide-wrapped titanium dioxide microsphere material, in particular to a preparation method of a graphene oxide-wrapped titanium dioxide microsphere photocatalyst.
背景技术Background technique
纳米级TiO2近年来引起了诸多的关注，广泛应用于光催化材料、太阳能电池、气敏传感器和光电子学器件等领域。就光催化研究而言，TiO2的光催化能力取决于其晶型、晶粒大小以及结晶程度，相对而言，结晶度较高、晶粒较小的锐钛矿相的纳米TiO2表现出更好的光催化性能。而电子-空穴复合、光子散射等都会影响到TiO2最终的光子利用效率。Nanoscale TiO 2 has attracted a lot of attention in recent years and is widely used in photocatalytic materials, solar cells, gas sensors and optoelectronic devices. As far as photocatalytic research is concerned, the photocatalytic ability of TiO 2 depends on its crystal form, grain size and crystallization degree. Better photocatalytic performance. The electron-hole recombination and photon scattering will affect the final photon utilization efficiency of TiO 2 .
石墨烯具有良好的导热性[3000W/(m·K)]、很高的强度（110GPa）和超大的比表面积（2630mz/g）。这些优异的性能使得石墨烯在纳米电子器件、气体传感器、能量存储及复合材料等领域应用前景广阔。Graphene has good thermal conductivity [3000W/(m K)], high strength (110GPa) and super large specific surface area (2630mz/g). These excellent properties make graphene have broad application prospects in the fields of nanoelectronic devices, gas sensors, energy storage and composite materials.
新型碳材料与TiO2复合形成复合材料，发挥了两者的协同作用，增强了材料对有机物、污染物的光催化性能，其原因有以下几点：（1）复合材料更大的比表面积提高了材料对有机污染物的吸附能力；（2）碳材料-TiO2界面异质结的形成改善了光生电子与空穴间的复合；（3）相比于纯TiO2，复合材料的费米能级可能向更正的方向偏移，进而提高了对更长波长光子的利用率；（4）碳材料表面吸收光子后，将电子注入到TiO2导带，形成用以降解有机污染物的反应激子（超氧自由基O2-和羟基自由基HO）。现有的微球光催化材料具有诸多的缺点，例如常规的TiO2具有较宽的帯隙（锐钛矿型TiO2的禁带宽度为3.2eV）、光生电子空穴对易于复合，并且较小的比表面积而仅有较低的染料吸附容量，这些严重限制了微球光催化产业的大力发展。The new carbon material and TiO 2 are combined to form a composite material, which exerts the synergistic effect of the two and enhances the photocatalytic performance of the material on organic matter and pollutants. The reasons are as follows: (1) The larger specific surface area of the composite material increases (2) The formation of carbon material-TiO 2 interface heterojunction improves the recombination between photogenerated electrons and holes; (3) Compared with pure TiO 2 , the Fermi The energy level may shift to the correct direction, thereby improving the utilization of longer wavelength photons; (4) After the surface of the carbon material absorbs photons, electrons are injected into the conduction band of TiO 2 to form a reaction to degrade organic pollutants Exciton (superoxide radical O2- and hydroxyl radical HO). The existing microsphere photocatalytic materials have many disadvantages, such as conventional TiO 2 has a wide band gap (the forbidden band width of anatase TiO 2 is 3.2eV), photogenerated electron-hole pairs are easy to recombine, and relatively The small specific surface area and only low dye adsorption capacity severely limit the vigorous development of the microsphere photocatalytic industry.
发明内容Contents of the invention
本发明的目的是提供一种氧化石墨烯包裹二氧化钛微球光催化剂的制备方法，解决了现有微球光催化材料帯隙较宽导致应用受限的问题。The purpose of the present invention is to provide a method for preparing a graphene oxide-wrapped titanium dioxide microsphere photocatalyst, which solves the problem that the existing microsphere photocatalytic material has a wide gap leading to limited application.
本发明所采用的技术方案是，一种氧化石墨烯包裹二氧化钛微球光催化剂的制备方法，具体按照以下步骤实施：The technical scheme adopted in the present invention is a preparation method of a graphene oxide-wrapped titanium dioxide microsphere photocatalyst, which is specifically implemented according to the following steps:
步骤1：在干燥的烧杯中加入质量浓度为98%的浓硫酸，冷却至0℃，搅拌中依次加入天然鳞片石墨、硝酸钠、高锰酸钾；控制反应温度为10～30℃，搅拌3h，然后将盛有混合溶液的烧杯置于35℃恒温水浴中，待反应温度升至35℃继续搅拌30min，最后控制反应温度在0-100℃，滴加去离子水，继续搅拌30min，最后加入30%的双氧水和去离子水组成的混合溶液，离心水洗得到黄褐色泥状物；Step 1: Add concentrated sulfuric acid with a mass concentration of 98% into a dry beaker, cool to 0°C, add natural flake graphite, sodium nitrate, and potassium permanganate in turn while stirring; control the reaction temperature at 10-30°C, and stir for 3 hours , then put the beaker containing the mixed solution in a constant temperature water bath at 35°C, and continue to stir for 30 minutes when the reaction temperature rises to 35°C, and finally control the reaction temperature at 0-100°C, add deionized water dropwise, continue to stir for 30 minutes, and finally add A mixed solution composed of 30% hydrogen peroxide and deionized water was centrifuged and washed to obtain a yellow-brown mud;
步骤2：将步骤1得到的泥状物干燥，分散在去离子水中，超声1～3h，离心两次得到红褐色上清液；Step 2: Dry the sludge obtained in Step 1, disperse it in deionized water, sonicate for 1-3 hours, and centrifuge twice to obtain a reddish-brown supernatant;
步骤3：将浓度为0.5mmol/L的KCl溶液加入到无水乙醇中，磁力搅拌30min，缓慢滴入钛酸正丁酯，剧烈搅拌反应30min，陈化4h，离心分离并用无水乙醇和去离子水依次清洗，干燥得到白色粉体；Step 3: Add KCl solution with a concentration of 0.5mmol/L to absolute ethanol, stir magnetically for 30min, slowly drop n-butyl titanate, stir vigorously for 30min, age for 4h, centrifuge and dehydrate with absolute ethanol Ionized water was washed successively, and dried to obtain a white powder;
步骤4：将步骤2得到的上清液和步骤3得到的白色粉体混合，在室温条件，磁力搅拌24h，离心并水洗4次，得到灰白色粉体；Step 4: Mix the supernatant obtained in step 2 with the white powder obtained in step 3, stir magnetically for 24 hours at room temperature, centrifuge and wash 4 times with water to obtain an off-white powder;
步骤5：将步骤4得到的灰白色粉体置于马弗炉中，在真空的条件下，控制升温速率为1℃/min，保温2h得到氧化石墨烯包裹二氧化钛微球光催化剂。Step 5: Place the off-white powder obtained in Step 4 in a muffle furnace, and under vacuum conditions, control the heating rate to 1° C./min, and keep it warm for 2 hours to obtain a graphene oxide-wrapped titanium dioxide microsphere photocatalyst.
本发明的特点还在于，The present invention is also characterized in that,
其中的步骤1中天然鳞片石墨、硝酸钠、高锰酸钾的质量-体积浓度分别为：43.48g/L、43.48g/L、130.43g/L。The mass-volume concentrations of natural flake graphite, sodium nitrate, and potassium permanganate in step 1 are 43.48g/L, 43.48g/L, and 130.43g/L, respectively.
其中的步骤1中双氧水和去离子水的体积比为1：1～10。The volume ratio of hydrogen peroxide and deionized water in step 1 is 1:1-10.
其中的步骤1中去离子水的滴加速度为0.3～0.5mL/秒。The dropping rate of the deionized water in step 1 is 0.3-0.5mL/sec.
其中的步骤2中泥状物与去离子水的体积比是1：1000～125。The volume ratio of sludge to deionized water in step 2 is 1:1000-125.
其中的步骤3中KCl溶液与无水乙醇的体积比是1：300～200，KCl溶液与钛酸正丁酯的体积比是1：5～2。In step 3, the volume ratio of KCl solution to absolute ethanol is 1:300-200, and the volume ratio of KCl solution to n-butyl titanate is 1:5-2.
其中的步骤4中上清液和白色粉体的比例是200：1～1000：1mL/g。The ratio of supernatant liquid to white powder in step 4 is 200:1-1000:1mL/g.
本发明的有益效果是：本发明采用简单实用的方法，将氧化石墨烯和二氧化钛稳定的结合在一起。实验周期短，便于操作，具有合成速度快、效率高和能耗低的优点，极具有工业化生产的前景。The beneficial effects of the invention are: the invention uses a simple and practical method to stably combine graphene oxide and titanium dioxide. The experiment cycle is short, easy to operate, has the advantages of fast synthesis speed, high efficiency and low energy consumption, and has great prospects for industrial production.
利用石墨烯的巨大的比表面积可以大大提高复合光催化剂的染料吸附容量，二维结构优异的电导性能可以极大地提高光生电子和空穴的传递、转移，提高分离效率，并且石墨烯在复合光催化剂中所产生的杂质能级效应可以大大的削减复合材料的禁带宽度为优异的光催化性能打下坚实的基础。此外，石墨烯所具有的优异的力学性能可以维持复合材料的特殊的结构，这在一定程度上为复合催化的实现提供了物质基础。Utilizing the huge specific surface area of graphene can greatly improve the dye adsorption capacity of the composite photocatalyst, the excellent electrical conductivity of the two-dimensional structure can greatly improve the transmission and transfer of photogenerated electrons and holes, and improve the separation efficiency, and graphene can be used in composite photocatalysts. The impurity energy level effect produced in the catalyst can greatly reduce the bandgap width of the composite material and lay a solid foundation for excellent photocatalytic performance. In addition, the excellent mechanical properties of graphene can maintain the special structure of composite materials, which provides a material basis for the realization of composite catalysis to a certain extent.
附图说明Description of drawings
图1是本发明实施例1制得的氧化石墨烯包裹二氧化钛微球光催化剂的一系列扫描电镜照片，其中，a是氧化石墨放大18000倍的扫描电镜照片，b是二氧化钛微球放大120000的扫描电镜照片；c是氧化石墨烯包裹二氧化钛微球的透射电镜照片，对应的标尺为100nm；d是氧化石墨烯包裹二氧化钛微球的透射电镜照片，对应的标尺为5nm；Figure 1 is a series of scanning electron micrographs of the graphene oxide-wrapped titanium dioxide microsphere photocatalyst prepared in Example 1 of the present invention, wherein a is a scanning electron micrograph of graphite oxide magnified 18,000 times, and b is a scan of titanium dioxide microspheres magnified 120,000 Electron microscope photo; c is a transmission electron microscope photo of graphene oxide-wrapped titanium dioxide microspheres, and the corresponding scale is 100nm; d is a transmission electron microscope photo of graphene oxide-wrapped titanium dioxide microspheres, and the corresponding scale is 5nm;
图2是本发明实施例2完成氧化石墨烯包裹二氧化钛过程中一系列产物的红外光谱，其中曲线a是氧化石墨烯的红外光谱曲线，曲线b是纯二氧化钛的红外光谱曲线，曲线c是氧化石墨烯包裹二氧化钛微球的红外光谱曲线；Fig. 2 is the infrared spectrum of a series of products in the process of completing graphene oxide wrapping titanium dioxide in Example 2 of the present invention, wherein curve a is the infrared spectrum curve of graphene oxide, curve b is the infrared spectrum curve of pure titanium dioxide, and curve c is graphite oxide Infrared spectrum curve of ene-wrapped titanium dioxide microspheres;
图3是本发明实施例3制得氧化石墨烯包裹二氧化钛微球材料的光催化图，其中，a是在紫外光照射条件下所得；b是在可见光照射条件下所得。3 is a photocatalytic diagram of the graphene oxide-wrapped titanium dioxide microsphere material obtained in Example 3 of the present invention, wherein a is obtained under ultraviolet light irradiation conditions; b is obtained under visible light irradiation conditions.
具体实施方式Detailed ways
下面结合附图和具体实施方式对本发明进行详细说明。The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.
本发明氧化石墨烯包裹二氧化钛微球光催化剂，形貌均一，氧化石墨烯的包裹厚度可方便控制，不会脱落，单分散良好，微球的直径为500nm左右，氧化石墨烯片层的大小可以通过超声时间来控制，包裹层数可以通过时间和浓度调节。The graphene oxide-wrapped titanium dioxide microsphere photocatalyst of the present invention has a uniform appearance, and the wrapping thickness of the graphene oxide can be conveniently controlled without falling off, and the monodispersity is good, the diameter of the microsphere is about 500nm, and the size of the graphene oxide sheet can be Controlled by ultrasonic time, the number of coating layers can be adjusted by time and concentration.
本发明制备氧化石墨烯包裹二氧化钛微球光催化剂的方法，具体按照以下步骤进行：The method for preparing the graphene oxide-wrapped titanium dioxide microsphere photocatalyst of the present invention is specifically carried out according to the following steps:
步骤1：在干燥的烧杯中加入质量浓度为98%的浓硫酸，冷却至约0℃，搅拌中依次加入天然鳞片石墨，硝酸钠，高锰酸钾。其中天然鳞片石墨、硝酸钠、高锰酸钾的质量-体积浓度分别为：43.48g/L，43.48g/L和130.43g/L。Step 1: Add concentrated sulfuric acid with a mass concentration of 98% into a dry beaker, cool to about 0°C, and add natural flake graphite, sodium nitrate, and potassium permanganate in sequence while stirring. The mass-volume concentrations of natural flake graphite, sodium nitrate and potassium permanganate are 43.48g/L, 43.48g/L and 130.43g/L respectively.
控制反应温度为10～30℃，搅拌3h，然后将上述溶液烧杯置于35℃左右的恒温水浴中，待反应温度升至35℃左右继续搅拌30min。最后控制反应温度在100℃以内，滴加去离子水，继续搅拌30min，滴加速度为0.3～0.5mL/秒。最后加入适量30%双氧水和去离子水组成的混合溶液。加入的双氧水、去离子水的比例是1：1～1：10。趁热离心水洗得到黄褐色泥状物。Control the reaction temperature at 10-30°C, stir for 3 hours, then place the beaker of the above solution in a constant temperature water bath at about 35°C, and continue stirring for 30 minutes when the reaction temperature rises to about 35°C. Finally, control the reaction temperature within 100°C, add deionized water dropwise, and continue to stir for 30 minutes, with a dropping rate of 0.3-0.5mL/s. Finally, a mixed solution composed of an appropriate amount of 30% hydrogen peroxide and deionized water was added. The ratio of hydrogen peroxide and deionized water added is 1:1~1:10. Centrifuge and wash with water while hot to obtain a yellow-brown mud.
步骤2：将上述泥状物干燥，称取0.2g分散在去离子水中，然后持续超声，最后离心两次取出红褐色上清液。超声时间为1～3h。泥状物与去离子水的体积比是1：1000～1：125。Step 2: Dry the above mud, weigh 0.2g and disperse it in deionized water, then continue to sonicate, and finally centrifuge twice to take out the reddish-brown supernatant. Ultrasonic time is 1 ~ 3h. The volume ratio of sludge to deionized water is 1:1000～1:125.
步骤3：将1.5mL浓度为0.5mmol/L KCl溶液加入到300mL无水乙醇中，磁力搅拌30min，缓慢滴入5.4mL的钛酸正丁酯，剧烈搅拌反应30min，陈化4h，离心分离并用无水乙醇和去离子水依次清洗，干燥得到一种纯白色的粉体。KCl溶液与无水乙醇的体积比是1：300～200，KCl溶液与钛酸正丁酯的体积比是1：5～2。Step 3: Add 1.5mL of 0.5mmol/L KCl solution into 300mL of absolute ethanol, stir magnetically for 30min, slowly drop in 5.4mL of n-butyl titanate, stir vigorously for 30min, age for 4h, centrifuge and use Wash with absolute ethanol and deionized water in sequence, and dry to obtain a pure white powder. The volume ratio of KCl solution to absolute ethanol is 1:300-200, and the volume ratio of KCl solution to n-butyl titanate is 1:5-2.
步骤4：将步骤2中所得的上清液和步骤3中的白色粉体混合，在室温的条件下，持续磁力搅拌24h，最后离心并水洗4次，得到灰白色粉体。上清液和白色粉体的比例是200：1～1000：1mL/g。Step 4: Mix the supernatant obtained in step 2 with the white powder in step 3, and continue magnetic stirring for 24 hours at room temperature, and finally centrifuge and wash 4 times with water to obtain an off-white powder. The ratio of supernatant to white powder is 200:1-1000:1mL/g.
步骤5：将步骤4中所得灰白色粉体置于马弗炉中，在真空的条件下，合理控制升温速率1℃/min和保温2h得到浅灰色粉体，即氧化石墨烯包裹二氧化钛微球光催化剂。Step 5: Place the off-white powder obtained in step 4 in a muffle furnace. Under vacuum conditions, reasonably control the heating rate of 1°C/min and keep warm for 2 hours to obtain a light gray powder, that is, graphene oxide-wrapped titanium dioxide microspheres. catalyst.
本发明中浓硫酸和高锰酸钾的用量，以及低温中温和高温反应的温度控制，以及水的加入量都会影响氧化石墨的质量，以及氧化石墨的层间距。最终影响氧化石墨烯的尺寸和层数。The consumption of concentrated sulfuric acid and potassium permanganate in the present invention, and the temperature control of low-temperature, medium-temperature and high-temperature reaction, and the addition amount of water all can affect the quality of graphite oxide, and the interlayer spacing of graphite oxide. Ultimately affect the size and number of layers of graphene oxide.
本发明中的煅烧时间和升温速率会影响氧化石墨烯包裹二氧化钛微球的完整性，过长的煅烧时间和过快的升温速率会导致氧化石墨烯包裹二氧化钛微球的微观形貌受到破坏。The calcination time and heating rate in the present invention will affect the integrity of the graphene oxide-wrapped titanium dioxide microspheres, and too long calcination time and too fast heating rate will cause the microscopic morphology of the graphene oxide-wrapped titanium dioxide microspheres to be destroyed.
实施例1Example 1
在干燥的烧杯中加入98%的浓硫酸115mL，冷却至约0℃，搅拌中依次加入天然鳞片石墨5g，硝酸钠5g，高锰酸钾15g。控制反应温度为10～30℃，搅拌3h，然后将上述溶液烧杯置于35℃左右的恒温水浴中，待反应温度升至35℃左右继续搅拌30min。最后控制反应温度在100℃以内，滴加去离子水，继续搅拌30min，滴加速度为0.3～0.5mL/秒。最后加入适量30%双氧水和50mL去离子水组成的混合溶液。加入的双氧水、去离子水的比例是1：5。趁热离心水洗得到黄褐色泥状物。将上述泥状物干燥，称取0.2g分散在去离子水中，然后持续超声3h，最后离心两次取出红褐色上清液。超声时间为1～3h。泥状物与去离子水的比例是1：125。将1.5mL浓度为0.5mmol/L KCl溶液加入到300mL无水乙醇中，磁力搅拌30min，缓慢滴入5.4mL的钛酸正丁酯，剧烈搅拌反应30min，陈化4h，离心分离并用无水乙醇和去离子水依次清洗，干燥得到一种纯白色的粉体。KCl溶液、无水乙醇、钛酸正丁酯的比例是1：300：5。将上述所得的上清液和步骤3中的白色粉体混合，在室温的条件下，持续磁力搅拌24h，最后离心并水洗4次，得到灰白色粉体。上清液和白色粉体的比例是多少1000：1mL/g。将上述所得灰白色粉体置于马弗炉中，在真空的条件下，合理控制升温速率1℃/min和保温2h得到浅灰色粉体。从图1中可以看出，所制备的氧化石墨烯包裹二氧化钛微球，形貌均一，分散良好微球的直径为500nm左右。氧化石墨烯包裹没有发生脱落。Add 115mL of 98% concentrated sulfuric acid into a dry beaker, cool to about 0°C, add 5g of natural flake graphite, 5g of sodium nitrate, and 15g of potassium permanganate in sequence while stirring. Control the reaction temperature at 10-30°C, stir for 3 hours, then place the beaker of the above solution in a constant temperature water bath at about 35°C, and continue stirring for 30 minutes until the reaction temperature rises to about 35°C. Finally, control the reaction temperature within 100°C, add deionized water dropwise, and continue to stir for 30 minutes, with a dropping rate of 0.3-0.5mL/s. Finally, a mixed solution consisting of an appropriate amount of 30% hydrogen peroxide and 50 mL of deionized water was added. The ratio of hydrogen peroxide and deionized water added is 1:5. Centrifuge and wash with water while hot to obtain a yellow-brown mud. Dry the above mud, weigh 0.2 g and disperse it in deionized water, then continue to sonicate for 3 hours, and finally centrifuge twice to take out the reddish-brown supernatant. Ultrasonic time is 1 ~ 3h. The ratio of sludge to deionized water is 1:125. Add 1.5mL of 0.5mmol/L KCl solution into 300mL of absolute ethanol, stir magnetically for 30min, slowly drop in 5.4mL of n-butyl titanate, stir vigorously for 30min, age for 4h, centrifuge and wash with absolute ethanol and deionized water were washed successively, and dried to obtain a pure white powder. The ratio of KCl solution, absolute ethanol, and n-butyl titanate is 1:300:5. Mix the above-obtained supernatant with the white powder in step 3, continue magnetic stirring for 24 hours at room temperature, and finally centrifuge and wash with water 4 times to obtain an off-white powder. What is the ratio of supernatant to white powder 1000:1mL/g. The gray-white powder obtained above was placed in a muffle furnace, and under vacuum conditions, the heating rate was reasonably controlled at 1° C./min and the temperature was kept for 2 hours to obtain a light gray powder. It can be seen from Figure 1 that the prepared graphene oxide-wrapped titanium dioxide microspheres have a uniform appearance, and the diameter of the well-dispersed microspheres is about 500 nm. The graphene oxide package did not fall off.
实施例2Example 2
在干燥的烧杯中加入98%的浓硫酸115mL，冷却至约0℃，搅拌中依次加入天然鳞片石墨5g，硝酸钠5g，高锰酸钾15g。控制反应温度为10～30℃，搅拌3h，然后将上述溶液烧杯置于35℃左右的恒温水浴中，待反应温度升至35℃左右继续搅拌30min。最后控制反应温度在100℃以内，滴加去离子水，继续搅拌30min，滴加速度为0.3～0.5mL/秒。最后加入适量30%双氧水和50mL去离子水组成的混合溶液。加入的双氧水、去离子水的比例是1：1。趁热离心水洗得到黄褐色泥状物。将上述泥状物干燥，称取0.2g分散在去离子水中，然后持续超声3h，最后离心两次取出红褐色上清液。超声时间为1～3h。泥状物与去离子水的比例是1：500。将1.5mL浓度为0.5mmol/L KCl溶液加入到300mL无水乙醇中，磁力搅拌30min，缓慢滴入5.4mL的钛酸正丁酯，剧烈搅拌反应30min，陈化4h，离心分离并用无水乙醇和去离子水依次清洗，干燥得到一种纯白色的粉体。KCl溶液、无水乙醇、钛酸正丁酯的比例是1：600：10。将上述所得的上清液和步骤3中的白色粉体混合，在室温的条件下，持续磁力搅拌24h，最后离心并水洗4次，得到灰白色粉体。上清液和白色粉体的比例是多少500：1mL/g。将上述所得灰白色粉体置于马弗炉中，在真空的条件下，合理控制升温速率1℃/min和保温2h得到浅灰色粉体。从图2中可以看出，所制备的氧化石墨烯包裹二氧化钛微球，过程中一系列中间产物都完全达到要求，对应的红外光谱表明其制备过程发生酯化反应键合，使二氧化钛和氧化石墨烯紧密的结合起来。Add 115mL of 98% concentrated sulfuric acid into a dry beaker, cool to about 0°C, add 5g of natural flake graphite, 5g of sodium nitrate, and 15g of potassium permanganate in sequence while stirring. Control the reaction temperature at 10-30°C, stir for 3 hours, then place the beaker of the above solution in a constant temperature water bath at about 35°C, and continue stirring for 30 minutes when the reaction temperature rises to about 35°C. Finally, control the reaction temperature within 100°C, add deionized water dropwise, and continue to stir for 30 minutes, with a dropping rate of 0.3-0.5mL/s. Finally, a mixed solution consisting of an appropriate amount of 30% hydrogen peroxide and 50 mL of deionized water was added. The ratio of hydrogen peroxide and deionized water added is 1:1. Centrifuge and wash with water while hot to obtain a yellow-brown mud. Dry the above mud, weigh 0.2 g and disperse it in deionized water, then continue to sonicate for 3 hours, and finally centrifuge twice to take out the reddish-brown supernatant. Ultrasonic time is 1 ~ 3h. The ratio of sludge to deionized water is 1:500. Add 1.5mL of 0.5mmol/L KCl solution into 300mL of absolute ethanol, stir magnetically for 30min, slowly drop in 5.4mL of n-butyl titanate, stir vigorously for 30min, age for 4h, centrifuge and wash with absolute ethanol and deionized water were washed successively, and dried to obtain a pure white powder. The ratio of KCl solution, absolute ethanol, and n-butyl titanate is 1:600:10. Mix the above-obtained supernatant with the white powder in step 3, continue magnetic stirring for 24 hours at room temperature, and finally centrifuge and wash with water 4 times to obtain an off-white powder. What is the ratio of supernatant to white powder 500:1mL/g. The gray-white powder obtained above was placed in a muffle furnace, and under vacuum conditions, the heating rate was reasonably controlled at 1° C./min and the temperature was kept for 2 hours to obtain a light gray powder. As can be seen from Figure 2, the prepared graphene oxide wraps titanium dioxide microspheres, and a series of intermediate products in the process fully meet the requirements. The corresponding infrared spectrum shows that the esterification reaction bonding occurs during the preparation process, so that titanium dioxide and graphite oxide Alkenes are tightly bound.
实施例3Example 3
在干燥的烧杯中加入98%的浓硫酸115mL，冷却至约0℃，搅拌中依次加入天然鳞片石墨5g，硝酸钠5g，高锰酸钾15g。控制反应温度为10～30℃，搅拌3h，然后将上述溶液烧杯置于35℃左右的恒温水浴中，待反应温度升至35℃左右继续搅拌30min。最后控制反应温度在100℃以内，滴加去离子水，继续搅拌30min，滴加速度为0.3～0.5mL/秒。最后加入适量30%双氧水和50mL去离子水组成的混合溶液。加入的双氧水、去离子水的比例是1：10。趁热离心水洗得到黄褐色泥状物。将上述泥状物干燥，称取0.2g分散在去离子水中，然后持续超声3h，最后离心两次取出红褐色上清液。超声时间为1～3h。泥状物与去离子水的比例是1：1000。将1.5mL浓度为0.5mmol/LKCl溶液加入到300mL无水乙醇中，磁力搅拌30min，缓慢滴入5.4mL的钛酸正丁酯，剧烈搅拌反应30min，陈化4h，离心分离并用无水乙醇和去离子水依次清洗，干燥得到一种纯白色的粉体。KCl溶液、无水乙醇、钛酸正丁酯的比例是2：1000：10。将上述所得的上清液和步骤3中的白色粉体混合，在室温的条件下，持续磁力搅拌24h，最后离心并水洗4次，得到灰白色粉体。上清液和白色粉体的比例是多少600：1mL/g。将上述所得灰白色粉体置于马弗炉中，在真空的条件下，合理控制升温速率1℃/min和保温2h得到浅灰色粉体。从图3中可以看出，所制备的氧化石墨烯包裹二氧化钛微球，其光催化能力很强，在可见光条件下，短时间可以降解有机物。Add 115mL of 98% concentrated sulfuric acid into a dry beaker, cool to about 0°C, add 5g of natural flake graphite, 5g of sodium nitrate, and 15g of potassium permanganate in sequence while stirring. Control the reaction temperature at 10-30°C, stir for 3 hours, then place the beaker of the above solution in a constant temperature water bath at about 35°C, and continue stirring for 30 minutes when the reaction temperature rises to about 35°C. Finally, control the reaction temperature within 100°C, add deionized water dropwise, and continue to stir for 30 minutes, with a dropping rate of 0.3-0.5mL/sec. Finally, a mixed solution consisting of an appropriate amount of 30% hydrogen peroxide and 50 mL of deionized water was added. The ratio of hydrogen peroxide and deionized water added is 1:10. Centrifuge and wash with water while hot to obtain a yellow-brown mud. Dry the above mud, weigh 0.2 g and disperse it in deionized water, then continue to sonicate for 3 hours, and finally centrifuge twice to take out the reddish-brown supernatant. Ultrasonic time is 1 ~ 3h. The ratio of sludge to deionized water is 1:1000. Add 1.5 mL of 0.5 mmol/L KCl solution into 300 mL of absolute ethanol, stir magnetically for 30 min, slowly drop in 5.4 mL of n-butyl titanate, stir vigorously for 30 min, age for 4 h, centrifuge and wash with absolute ethanol and The deionized water was washed successively, and dried to obtain a pure white powder. The ratio of KCl solution, absolute ethanol, and n-butyl titanate is 2:1000:10. Mix the above-obtained supernatant with the white powder in step 3, continue magnetic stirring for 24 hours at room temperature, and finally centrifuge and wash with water 4 times to obtain an off-white powder. What is the ratio of supernatant to white powder 600:1mL/g. The gray-white powder obtained above was placed in a muffle furnace, and under vacuum conditions, the heating rate was reasonably controlled at 1° C./min and the temperature was kept for 2 hours to obtain a light gray powder. It can be seen from Figure 3 that the prepared graphene oxide-wrapped titanium dioxide microspheres have a strong photocatalytic ability and can degrade organic matter in a short time under visible light conditions.
实施例4Example 4
在干燥的烧杯中加入98%的浓硫酸115mL，冷却至约0℃，搅拌中依次加入天然鳞片石墨5g，硝酸钠5g，高锰酸钾15g。控制反应温度为10～30℃，搅拌3h，然后将上述溶液烧杯置于35℃左右的恒温水浴中，待反应温度升至35℃左右继续搅拌30min。最后控制反应温度在100℃以内，滴加去离子水，继续搅拌30min，滴加速度为0.3～0.5mL/秒。最后加入适量30%双氧水和50mL去离子水组成的混合溶液。加入的双氧水、去离子水的比例是1：4。趁热离心水洗得到黄褐色泥状物。将上述泥状物干燥，称取0.2g分散在去离子水中，然后持续超声3h，最后离心两次取出红褐色上清液。超声时间为1～3h。泥状物与去离子水的比例是1：900。将1.5mL浓度为0.5mmol/L KCl溶液加入到300mL无水乙醇中，磁力搅拌30min，缓慢滴入5.4mL的钛酸正丁酯，剧烈搅拌反应30min，陈化4h，离心分离并用无水乙醇和去离子水依次清洗，干燥得到一种纯白色的粉体。KCl溶液、无水乙醇、钛酸正丁酯的比例是1：200：2。将上述所得的上清液和步骤3中的白色粉体混合，在室温的条件下，持续磁力搅拌24h，最后离心并水洗4次，得到灰白色粉体。上清液和白色粉体的比例是多少200：1mL/g。将上述所得灰白色粉体置于马弗炉中，在真空的条件下，合理控制升温速率1℃/min和保温2h得到浅灰色粉体。Add 115mL of 98% concentrated sulfuric acid into a dry beaker, cool to about 0°C, add 5g of natural flake graphite, 5g of sodium nitrate, and 15g of potassium permanganate in sequence while stirring. Control the reaction temperature at 10-30°C, stir for 3 hours, then place the beaker of the above solution in a constant temperature water bath at about 35°C, and continue stirring for 30 minutes when the reaction temperature rises to about 35°C. Finally, control the reaction temperature within 100°C, add deionized water dropwise, and continue to stir for 30 minutes, with a dropping rate of 0.3-0.5mL/sec. Finally, a mixed solution consisting of an appropriate amount of 30% hydrogen peroxide and 50 mL of deionized water was added. The ratio of hydrogen peroxide and deionized water added is 1:4. Centrifuge and wash with water while hot to obtain a yellow-brown mud. Dry the above mud, weigh 0.2 g and disperse it in deionized water, then continue to sonicate for 3 hours, and finally centrifuge twice to take out the reddish-brown supernatant. Ultrasonic time is 1 ~ 3h. The ratio of sludge to deionized water is 1:900. Add 1.5mL of 0.5mmol/L KCl solution into 300mL of absolute ethanol, stir magnetically for 30min, slowly drop in 5.4mL of n-butyl titanate, stir vigorously for 30min, age for 4h, centrifuge and wash with absolute ethanol and deionized water were washed successively, and dried to obtain a pure white powder. The ratio of KCl solution, absolute ethanol, and n-butyl titanate is 1:200:2. Mix the above-obtained supernatant with the white powder in step 3, continue magnetic stirring for 24 hours at room temperature, and finally centrifuge and wash with water 4 times to obtain an off-white powder. What is the ratio of supernatant to white powder 200:1mL/g. The gray-white powder obtained above was placed in a muffle furnace, and under vacuum conditions, the heating rate was reasonably controlled at 1° C./min and the temperature was kept for 2 hours to obtain a light gray powder.
实施例5Example 5
在干燥的烧杯中加入98%的浓硫酸115mL，冷却至约0℃，搅拌中依次加入天然鳞片石墨5g，硝酸钠5g，高锰酸钾15g。控制反应温度为10～30℃，搅拌3h，然后将上述溶液烧杯置于35℃左右的恒温水浴中，待反应温度升至35℃左右继续搅拌30min。最后控制反应温度在100℃以内，滴加去离子水，继续搅拌30min，滴加速度为0.3～0.5mL/秒。最后加入适量30%双氧水和50mL去离子水组成的混合溶液。加入的双氧水、去离子水的比例是1：2。趁热离心水洗得到黄褐色泥状物。将上述泥状物干燥，称取0.2g分散在去离子水中，然后持续超声3h，最后离心两次取出红褐色上清液。超声时间为1～3h。泥状物与去离子水的比例是1：700。将1.5mL浓度为0.5mmol/L KCl溶液加入到300mL无水乙醇中，磁力搅拌30min，缓慢滴入5.4mL的钛酸正丁酯，剧烈搅拌反应30min，陈化4h，离心分离并用无水乙醇和去离子水依次清洗，干燥得到一种纯白色的粉体。KCl溶液、无水乙醇、钛酸正丁酯的比例是4：500：5。将上述所得的上清液和步骤3中的白色粉体混合，在室温的条件下，持续磁力搅拌24h，最后离心并水洗4次，得到灰白色粉体。上清液和白色粉体的比例是多少400：1mL/g。将上述所得灰白色粉体置于马弗炉中，在真空的条件下，合理控制升温速率1℃/min和保温2h得到浅灰色粉体。Add 115mL of 98% concentrated sulfuric acid into a dry beaker, cool to about 0°C, add 5g of natural flake graphite, 5g of sodium nitrate, and 15g of potassium permanganate in sequence while stirring. Control the reaction temperature at 10-30°C, stir for 3 hours, then place the beaker of the above solution in a constant temperature water bath at about 35°C, and continue stirring for 30 minutes when the reaction temperature rises to about 35°C. Finally, control the reaction temperature within 100°C, add deionized water dropwise, and continue to stir for 30 minutes, with a dropping rate of 0.3-0.5mL/s. Finally, a mixed solution consisting of an appropriate amount of 30% hydrogen peroxide and 50 mL of deionized water was added. The ratio of hydrogen peroxide and deionized water added is 1:2. Centrifuge and wash with water while hot to obtain a yellow-brown mud. Dry the above mud, weigh 0.2 g and disperse it in deionized water, then continue to sonicate for 3 hours, and finally centrifuge twice to take out the reddish-brown supernatant. Ultrasonic time is 1 ~ 3h. The ratio of sludge to deionized water is 1:700. Add 1.5mL of 0.5mmol/L KCl solution into 300mL of absolute ethanol, stir magnetically for 30min, slowly drop in 5.4mL of n-butyl titanate, stir vigorously for 30min, age for 4h, centrifuge and wash with absolute ethanol and deionized water were washed successively, and dried to obtain a pure white powder. The ratio of KCl solution, absolute ethanol, and n-butyl titanate is 4:500:5. Mix the above-obtained supernatant with the white powder in step 3, continue magnetic stirring for 24 hours at room temperature, and finally centrifuge and wash with water 4 times to obtain an off-white powder. What is the ratio of supernatant to white powder 400:1mL/g. The gray-white powder obtained above was placed in a muffle furnace, and under vacuum conditions, the heating rate was reasonably controlled at 1° C./min and the temperature was kept for 2 hours to obtain a light gray powder.
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| CN107185493B (en) * | 2017-06-28 | 2020-05-05 | 中国航发北京航空材料研究院 | Preparation method of graphene-modified composite mesoporous carbon microsphere air purifier |
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| CN109385159A (en) * | 2018-10-16 | 2019-02-26 | 上海申得欧有限公司 | A kind of photocatalysis exterior wall latex paint and preparation method thereof |
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| CN109346110A (en) * | 2018-10-29 | 2019-02-15 | 东北师范大学 | Carbon-based nanocomposite film for color holographic storage and method for making the same |
| CN109777245A (en) * | 2019-02-19 | 2019-05-21 | 安徽企服工程技术有限公司 | A kind of photocuring film forming coating for wall surface |
| WO2021019098A1 (en) | 2019-07-31 | 2021-02-04 | Anaphite Limited | Composite materials |
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